Siliceous fossils in sediments of the Ibero-Moroccan shelf and adjacent deep sea plains

Siliceous skeletons were investigated in two core profiles (9 cores), one off Cap de Sines, Portugal and the other off Cap de Mazagan, Morocco. Total number of skeletons was determined per gram of dried sediment at different core depths of the fraction >21 µ. Results are compared with a core profile from the Arabian Sea. Diatoms are of four groups: (A) marine-planktonic, B) marine-benthic, (C) freshwater and (D) Tertiary species (Trinacria e.g.). Species from groups (B), (C) and (D) are redeposited in all cores taken at a water depth of greater than 100 m. Small numbers of Silicoflagellates and Radiolarians were found throughout the cores from the Ibero-Moroccan shelf. In the Arabian Sea core, Radiolarians were concentrated in distinct horizons in which Tertiary material was redeposited (40-50, 140-150, 250-260 cm). The number of siliceous skeletons per gram of dried sediment decreases more or less rapidly with increasing depth in all cores. Whereas about 2500 skeletons were found in sediments close to the surface, approximately 100 skeletons only were found in deeper (>40 cm) layers. Deeper horizons with more than 100 specimens were interpreted as redeposited material. This sediment contained robust skeletons, resistant against dissolution, as well as benthic and Tertiary material. The decrease of siliceous skeletons relative to core depth depends upon the sedimentation rate. Where the sedimentation rate is high, the opal dissolution zone extends down to 30-60 cm, where the sedimentation rate is low, it is located at 10-30 cm. Below these depths opals disappears. These zones also have approximately the same age (4000 years) everywhere. Siliceous skeletons dissolve differentially, first the Silicoflagellates disappear, second the Diatoms, third the Radiolarians, and fourth the Sponge Spicules. Surface structure of skeletons from near the opal dissolution zones are similar to those of skeletons treated with NaOH. Tertiary diatoms (Trinacria e. g.) and benthic diatoms (Campylodiscus e.g.) dissolve less rapidly than skeletons of modern planktonic diatoms (Coscinodiscus e.g.). The time control of the opal dissolution zones appeared rather independent of various oceanic influences. No evidence was found for effects from upwelling either off Portugal or off Morocco. No difference in dissolution rates was recorded between the abyssal plains lying off these two areas. Likewise, there was no change in solution rates from Pleistocene to Holocene within either one of the abyssal plains. The Mediterranean outflow, which is enriched in dissolved silica, apparently had no effect on dissolution rates of siliceous skeletons in the sediment.

Sea-surface reconstruction of the east-equatorial South Atlantic

In order to reconstruct Late Quatemary variations of surface oceanography in the eastequatorial South Atlantic, time series of sea-surface temperatures (SST) and paleoproductivity were established from cores recovered in the Guinea and Angola Basins, and at the Walvis Ridge. These records, based on sedimentary alkenone and organic carbon concentrations, reveal that during the last 350,000 years surface circulation and productivity changes in the east-equatorial South Atlantic were highiy sensitive to climate forcing at 23- and 100-kyr periodicities. Covarying SST and paleoproductivity changes at the equator and at the Walvis Ridge appear to be driven by variations in zonal trade-wind intensity, which forces intensification or reduction of coastal and equatorial upwelling, as well as enhanced Benguela cold water advection from the South. Phase relationships of precessional variations in the paleoproductivity and SST records from the distinct sites were evaluated with respect to boreal summer insolation over Africa, movements of southem ocean thermal fronts, and changes in global ice volume. The 23-kyr phasing implies a sensitivity of eastem South Atlantic surface water advection and upwelling to West African monsoon intensity and to changes in the position ofthe subtropical high pressure cell over the South Atlantic, both phenomena which modulate zonal strength of southeasterly trades. SST and productivity changes north of 20°S lack significant variance at the 41-kyr periodicity; and at the Walvis Ridge and the equator lead changes in ice volume. This may indicate that obliquity-driven clirnate change, characteristic for northem high latitudes, e.g fluctuations in continental ice masses, did not substantially influence subtropical and tropical surface circulation in the South Atlantic. At the 23-kyr cycle SST and productivity changes in the eastern Angola Basin lag those in the equatorial Atlantic and at the Walvis Ridge by about 3500 years. This lag is explained by variations in cross-equatorial surface water transport and west-east countercurrent retum flow modifying precessional variations of SST and productivity in the eastem Angola Basin relative to those in the mid South Atlantic area under the central field of zonal trade winds. Sea level-related shifts of upwelling cells in phase with global clirnate change may be also recorded in SST and productivity variability along the continental margin off Southwest Africa. They may account for the delay of the paleoceanogreaphic signal from continental margin sites with respect to that from the pelagic sites at the equator and the Walvis Ridge.

Sea surface temperatur reconstruction for ODP Site 108-662

The record of planktonic foraminifer abundances at Site 662 during the late Pliocene (~1.7-2.1 Ma) was examined to determine variations in estimated sea-surface temperature (SST). We compared the results to SST estimates from a late Pleistocene record (~1.5-200 ka) from nearby piston core RC24-7. Within the primary orbital band (~20-100 k.y.), the cold-season responses of both equatorial Atlantic records are dominated by the precessional period, and the computed range of variability is quite similar. This is in contrast to the evolution of the dominant climatic response from 41 to 100 k.y. at high northern latitudes between the late Pliocene and the late Pleistocene. The orbital-band SST response in this region of greatest divergence in the equatorial Atlantic has not changed appreciably between the late Pliocene and the late Pleistocene.

(Table 1) Non-arboreal and arboreal pollen spectra at DSDP Holes 75-532 and 75-530A

Some samples from DSDP Holes 530A and 532 were analyzed for their fossil pollen content. The sites are located in the southeastern corner of the Angola Basin, about 200 km west of the present coastline. Fossil pollen assemblages of Holocene to Miocene age were compared with present-day pollen deposition in the arid Namib sand sea. The strong resemblance of all the pollen spectra indicates that very arid conditions existed in the coastal region of Namibia in Quaternary and Pliocene times. These data are in agreement with the late Miocene origin of the coastal aridity and with the conception that upwelling of cold water was responsible for these desert conditions.

Sedimentological and geochemical characteristics of upper Cretaceous and lower Tertiary sediments of ODP Hole 108-661A

Based on sedimentological and geochemical data, the Upper Cretaceous and Tertiary sequence at Ocean Drilling Program Site 661 was subdivided into four intervals: Interval I (Campanian age) is characterized by sediments deposited below the calcite compensation depth (CCD) inside a high-productivity area and well-oxygenated bottom waters, indicated by the absence of carbonate, the major occurrence of zeolites and opal-CT, and intense bioturbation. Very fine-grained siliciclastic sediments and the lack of any erosional features suggest a low-energy environment. The terrigenous fraction was probably supplied by winds from the nontropical areas in South Africa. Interval II (Maestrichtian age) is characterized by high-amplitude variations in the carbonate content indicative of a deposition above the CCD, superimposed by (climate-controlled) short-term fluctuations of the CCD. The absence of both zeolites and opal-CT imply a position of Site 661 outside high-productivity areas. The first occurrence of higher amounts of kaolinite (especially during the middle Maestrichtian) suggests the onset of a terrigenous sediment supply from tropical areas. Interval III (between uppermost Cretaceous to early Tertiary) is characterized by the absence of carbonate and zeolites, interpreted as deposition below the CCD and outside an oceanic high-productivity belt. The kaolinite-over-illite dominance suggests a terrigenous sediment supply from tropical areas. Interval IV (between early Tertiary and Miocene age) is characterized by the occurrence of black manganeserich layers, major nodules/pebbles, and erosional surfaces, indicating phases of extremely reduced sediment accumulation and bottom-current activities. In the lower part of this interval (?Eocene age), higher amounts of zeolites occur, which suggest a higher oceanic productivity caused by equatorial upwelling. The source area of the terrigenous sediment fraction at Site 661 was the tropical region of northwest Africa, as suggested by the kaolinite-over-illite dominance.

(Appendix 1) Age, Ge/Si ratio, aluminium and opal contents in ODP Sites 175-1081 and 175-1084

As a result of both culture and sediment core studies, the ratio of germanium (Ge) to silicon (Si) in diatom shells has been proposed as a proxy for monitoring whole-ocean changes in seawater Ge/Si, a ratio affected by changes in continental weathering. However, because of the difficulties of extracting and cleaning diatom frustules from deep-sea sediments, only samples from highly pure diatom oozes in the Antarctic region have been previously analyzed. Here we present data on diatom Ge/Si ratios, (Ge/Si)opal, for the time interval between 3.1 and 1.9 Ma from a mid-latitude, coastal upwelling area where significant terrigenous sediment input complicated the sample processing and analyses. In general, our (Ge/Si)opal values show the same decreasing trend after 2.6 Ma than previously measured in Antarctic sediments (Shemesh et al., 1989. Paleoceanography 4, 221-231), but with a noisier background that may reflect the local imprint of proximal continental input superimposed upon global changes in the ocean reservoir. The time of initiation of large-scale North Hemisphere glaciation at ~2.6 Ma is characterized by a declining pattern of diatom Ge/Si ratios, which could have resulted from a global increase in the input of riverine Si due to enhanced silica weathering and/or equatorward (northward) intrusions of subantarctic waters enriched in silica. High (Ge/Si)opal ratios are associated with high opal contents from the same sediment samples and with warm climate as indicated by depleted benthic foraminiferal d18O values from the North and Equatorial Atlantic. Cold periods signified by enriched benthic d18O values, on the contrary, are associated with lower (Ge/Si)opal ratios. We interpret diatom Ge/Si values to reflect the prevailing weathering state on the continents, with greater chemical weathering during warm and wet periods of the Pliocene and less during cooler and drier intervals.

Holocene d18O diatom from ODP Hole 178-1098A

The causes for rising temperatures along the Antarctic Peninsula during the late Holocene have been debated, particularly in light of instrumental records of warming over the past decades (Russell and McGregor, 2010, doi:10.1007/s10584-009-9673-4). Suggested mechanisms range from upwelling of warm deep waters onto the continental shelf in response to variations in the westerly winds (Bentley et al., 2009, doi:10.1177/0959683608096603), to an influence of El Niño-Southern Oscillation on sea surface temperatures (Shevenell et al., 2011, doi:10.1038/nature09751). Here, we present a record of Holocene glacial ice discharge, derived from the oxygen isotope composition of marine diatoms from Palmer Deep along the west Antarctic Peninsula continental margin. We assess atmospheric versus oceanic influences on glacial discharge at this location, using analyses of diatom geochemistry to reconstruct atmospherically forced glacial ice discharge and diatom assemblage (Taylor and Sjunneskog, 2002, doi:10.1029/2000PA000564) ecology to investigate the oceanic environment. We show that two processes of atmospheric forcing-an increasing occurrence of La Niña events (Makou et al., 2010, doi:10.1130/G30366.1) and rising levels of summer insolation-had a stronger influence during the late Holocene than oceanic processes driven by southern westerly winds and upwelling of upper Circumpolar Deepwater. Given that the evolution of El Niño-Southern Oscillation under global warming is uncertain (Yeh et al., 2009, doi:10.1038/nature08316), its future impacts on the climatically sensitive system of the Antarctic Peninsula Ice Sheet remain to be established.

Pliocene-Pleistocene oxygen isotope record DSDP Site 586, Ontong Java Plateau, Pacific Ocean i

Oceanographic changes in the western equatorial Pacific during the past 6 Ma are inferred from oxygen isotopic analyses of planktic and benthic foraminifera from Ontong Java Plateau (DSDP Site 586). The taxa are Globigerinoides sacculifer, Pulleniatina, Cibicidoides wuellerstorfi, and Oridorsalis umbonatus. Cooling and ice buildup are indicated by an 18O enrichment of 0.3 per mil in the planktic species near 3.4 Ma. This shift apparently is compensated in the benthic data by a warming of the deep waters by between 1° and 2° C. We suggest that the dominant source of upper deep water supply to the Pacific changed from Antarctic to North Atlantic at that time, the North Atlantic-derived water being warmer. Near 2.8 Ma (approximately) the planktic foraminifera again record an enrichment in 18O (Delta delta18O=0.25 per mil). We suggest ice buildup in the northern hemisphere as the cause, because of subsequent sharp increase in fluctuations of the delta18O signal, that is, instability. The enrichment is magnified in the benthic foraminifera (Delta delta18O = 0.5 per mil) by a cooling of the deep water by 1.5° at the time, presumably signalling a glacial-type reduction of North Atlantic Deep Water (NADW) production. Episodic divergence between the signals of G. sacculifer and Pulleniatina in the Pleistocene apparently reflects periods of increased upwelling in the western equatorial Pacific. The amplitude of ice volume fluctuations cannot be reconstructed from delta18O data alone, unless there are constraints on temperature variations. The increase in amplitude of fluctuation of the benthic and planktic signals during the Pleistocene may be attributed either to an increase in maximum ice volume, or to an increase in the fractionation of continental ice, or a combination of both causes.

Chemical composition of clay minerals from ODP Leg 168 sites

The exchangeable cation compositions of organic-poor terrigenous sediments containing smectite as primary ion exchanger from a series of holes along ODP Leg 168 transect on the eastern flank of the Juan de Fuca Ridge have been examined as a function of distance from the ridge axis and burial depth. The total cation exchange capacity (CEC) values of the sediments ranged from 2 to 59 meq/100 g, increasing with increases in the wt.% smectite. At the seafloor, the exchangeable cation compositions involving Na, K, Mg, and Ca, expressed in terms of equivalent fraction, are nearly constant regardless of the different transect sites: XNa = 0.21 ± 0.04, XK = 0.08 ± 0.01, XMg = 0.33 ± 0.09, and XCa = 0.38 ± 0.09. The calculated selectivity coefficients of the corresponding quaternary exchange reactions, calculated using porewater data, are in log units -5.45 ± 0.39 for Na, 1.97 ± 0.49 for K, 0.42 ± 0.41 for Mg, and 3.06 ± 0.69 for Ca. The exchangeable cation compositions below the seafloor change systematically with distance from the ridge crest and burial depth, conforming to the trends of the same cations in the porewaters. The selectivities for Na and Mg are roughly constant at temperatures from 2 to 66°C, indicating that the equivalent fractions of these two cations are independent of sediment alteration taking place on the ridge flank. Unlike Na and Mg, the temperature influence is significant for K and Ca, with Ca-selectivity decreases being coupled with increases in K-selectivity. Although potentially related to diagenetic and/or hydrothermal mineral precipitation or recrystallization, no evidence of such alteration was detected by XRD and TEM. In sites where upwelling of hydrothermal fluids from basement is occurring, the K-selectivity of the sediment is appreciably higher than at the other sites and corresponds to the formation of (Fe, Mg) rich smectite and zeolites. Our study indicates that local increases in K-selectivity at hydrothermal sites are caused by the formation of these authigenic minerals.

Stable isotope record of ODP Sites 108-658 and 108-659

Ocean Drilling Program Site 658, cored below a major upwelling cell offshore Cap Blanc, contains a largely undisturbed hemipelagic sediment section spanning the Brunhes Chron and the early Quaternary and late Pliocene. The companion Site 659 recovered a complete and undisturbed Neogene profile further offshore that serves as a nonupwelling pelagic reference section. Oxygen and carbon isotope ratios in benthic (C. wuellerstorfi and in part Uvigerina sp.) and planktonic foraminifers (G. inflata) provide a climatic record of high resolution for the Brunhes Chron. At Site 658 the record extends back to the early Pleistocene and late Pliocene. The standard oxygen isotope record of the last 730,000 yr is markedly refined by a well-documented high-frequency variation (e.g., by a new "aborted" ice age at stage 13.2 and by Younger-Dryas style climatic setbacks during most terminations). In the late Pliocene, the numerical oxygen isotope stage taxonomy was extended back to stage 137 about 3.3 Ma ago. In comparison with published records, stage 114 at 2.7 Ma represents the first major glaciation event, when 18O was short-term enriched up to a middle Pleistocene glacial d18O level. About 3.17 Ma ago (stage 133), the interglacial oxygen isotope values of C. wuellerstorfi started to increase by 0.5 per mil until 2.7 Ma and then remained largely constant until the Holocene. Based on the d13C difference between C. wuellerstorfi and G. inflata, the dissolved CO2 in the ambient bottom water of Site 658 was dominated by the flux of particulate carbon from the overlying upwelling cell during the last 630,000 yr. In contrast, the advection of (upper) North Atlantic Bottom Water dominated in the control of the local CO2 content during the early Pleistocene and late Pliocene.

Concentration of particulate matter and its dispersion factor in surface waters of the Canary upweling region, East Atlantic

Particulate matter concentration and water temperature at 5 m depth level are compared in the Canary upwelling region to the east of the Cape Blanc. It was found that accumulation of particulate matter was timed to hydrofrontal zones. Particle size distributions for particulate matter obtained using the Coulter counter agree with the hyperbolic law (of the Junge type) with double values for the size parameter, which changes for particle diameters of 5-6 microns. Average values for the size parameter in the region of the upwelling are significantly lower than in the open ocean. Specific surface of particulate matter associated with reactivity differs significantly on different sides of the upwelling front and increases beyond the upwelling.

Chert intervals in DSDP and ODP sites (Table 1)

Radiolarian cherts in the Tethyan realm of Jurassic age were recently interpreted as resulting from high biosiliceous productivity along upwelling zones in subequatorial paleolatitudes the locations of which were confirmed by revised paleomagnetic estimates. However, the widespread occurrence of cherts in the Eocene suggests that cherts may not always be reliable proxies of latitude and upwelling zones. In a new survey of the global spatio-temporal distribution of Cenozoic cherts in Deep Sea Drilling Project (DSDP) and Ocean Drilling Program (ODP) sediment cores, we found that cherts occur most frequently in the Paleocene and early Eocene, with a peak in occurrences at ~50 Ma that is coincident with the time of highest bottom water temperatures of the early Eocene climatic optimum (EECO) when the global ocean was presumably characterized by reduced upwelling efficiency and biosiliceous productivity. Cherts occur less commonly during the subsequent Eocene global cooling trend. Primary paleoclimatic factors rather than secondary diagenetic processes seem therefore to control chert formation. This timing of peak Eocene chert occurrence, which is supported by detailed stratigraphic correlations, contradicts currently accepted models that involve an initial loading of large amounts of dissolved silica from enhanced weathering and/or volcanism in a supposedly sluggish ocean of the EECO, followed during the subsequent middle Eocene global cooling by more vigorous oceanic circulation and consequent upwelling that made this silica reservoir available for enhanced biosilicification, with the formation of chert as a result of biosilica transformation during diagenesis. Instead, we suggest that basin-basin fractionation by deep-sea circulation could have raised the concentration of EECO dissolved silica especially in the North Atlantic, where an alternative mode of silica burial involving widespread direct precipitation and/or absorption of silica by clay minerals could have been operative in order to maintain balance between silica input and output during the upwelling-deficient conditions of the EECO. Cherts may therefore not always be proxies of biosiliceous productivity associated with latitudinally focused upwelling zones.

Cretaceous and Paleogene calcareous nannofossils from ODP Leg 123

Two of five holes drilled at two separate sites during Leg 123 of the Ocean Drilling Program intersected thick and relatively complete sections of Upper Cretaceous-Paleogene nannofossiliferous sediments. Although dominated by turbidite deposition in the upper part, Hole 765C contains a thick and relatively complete Albian-Oligocene section, including a particularly thick Aptian interval, with abundant and fairly well-preserved nannofossils. Several unconformities are confidently interpreted in this section that span much of the Santonian, late Campanian, Maestrichtian, late Eocene, and early Oligocene. Hole 766A contains a thick and relatively complete Albian-lower Eocene section having generally abundant and well-preserved nannofossils. Several unconformities also have been identified in this section that span much of the Coniacian, early Campanian, Maestrichtian, and late Eocene through early Pliocene. The chronostratigraphic position and length of all these unconformities may have considerable significance for reconstructing the sedimentary history and for interpreting the paleoceanography of this region. A particularly thick section of upper Paleocene-lower Eocene sediments, including a complete record across the Paleocene/Eocene boundary, also was cored in Hole 766A that contains abundant and diverse nannofossil assemblages. Although assemblages from this section were correlated successfully using a standard low-latitude zonation, difficulties were encountered that reduced biostratigraphic resolution. Several lines of evidence suggest a mid-latitude position for Site 766 during this time, including (1) high assemblage diversity characteristic of mid-latitude zones of upwelling and (2) absence of certain ecologically controlled markers found only in low latitudes.